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PART-D
IONIC EQUILLIBRIA
By :
S.K.Sinha
SINHA'S
IIT CHEMISTRY
Mo- 93149-05055
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
(a strong acid)
H+(aq)
(a strong acid)
Examples of bases:
1.
8.
NH3(aq) + H2O
2.
(a strong base)
acid1
base2
For examples:
1.
2.
3.
BH+
+
conjugate
acid2
H2O
base2
NH3 + H2O
base1
acid2
Aconjugate
base1
Cl-(aq)
conjugate
base1
H3O+(aq)
conjugate
acid2
C2H3O2-(aq);
conjugate
base1
NH4+(aq) + OH-(aq);
conjugate
conjugate
acid1
base2
In each reaction, a conjugate base is what remains of the acid molecule after it loses a
proton (H+), and a conjugate acid is what becomes of the base after it gains a proton.
acid1 - conjugate base1 and acid2 - conjugate base2 are called conjugate acid-base pairs;
they are a pair of species that are related to each other by the loss or gain of a single
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
is called hydronium
H3O+(aq) + Cl-(aq),
In reaction: HC2H3O2
H2O
H3O+(aq) + C2H3O2-(aq);
C2H3O2- is the stronger base; at equilibrium, a solution of acetic acid contains mostly
HC2H3O2 and a small amount of H3O+ and C2H3O2- ions.
NH4+(aq) + OH-(aq),
water is an acid. The competition for protons is between NH3 and OH-, in which OHis the strong base; the above equilibrium shifts to the left. That is, an aqueous
ammonia solution contains mostly NH3 molecule and a small amount of NH4OH,
NH4+, and OH-.
Exercises:
1.
2.
(a) H2PO4-;
(a) NH3
(b) H2C2O4;
(b) [Al(H2O)2(OH-)4]-
(c) [Al(H2O)6]3+;
(c) SO32-
(d) NH3;
(d) (CH3)3N:
(CH3)2COH+(acetone) + Cl-(acetone)
The degree of ionization in acetone increases in the order of HCl < HBr < HI. Based on this
observation, it was determined that the acidity of hydrogen halides increases down the
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
group: HF < HCl < HBr < HI. A similar trend of relative acidity is also observed for the
hydrides of Group VIA elements, such that, H2O < H2S < H2Se < H2Te.
For the same period hydrides, the relative acidity increases from left to right, such that:
CH4 < NH3 < H2O < HF;
Water is a stronger acid than ammonia, and in acid-base reaction, H2O acts as a BrnstedLowry acid, which donates a proton to NH3:
H2O(l) + NH3(aq)
NH4+(aq) + OH-(aq)
In reaction with HF, water acts as a Brnsted-Lowry base, which accept a proton:
HOSOH
HOPOH
OClOH
H
For these type of acids, their relative strengths depend on the electronegativity of
the central atoms. The more electronegative the central atom, the more polarized the OH
bond and the more readily it ionizes in aqueous solution to release the H+ ion. For
example, N, S, and Cl are more electronegative than P, and HNO3, H2SO4, and HClO4 are
stronger acids compared to H3PO4. The relative acid strengths are: HNO3 > H2SO4 > H3PO4.
For oxo-acids with central atoms from the same group, their relative strength decreases
from top to bottom as the electronegativity of the central atom decreases:
HOCl > HOBr > HOI;
For oxo-acids containing identical central atom, acidity increases as more oxygen atoms are
bonded to it. For example, acidity increases in the following order:
HOCl < HOClO < HOClO2 < HOClO3;
Oxygen is a very electronegative atom; when more oxygen atoms are bonded to the
central atom, the OH group in the molecule becomes more polarized (due to inductive
effect), and the more readily it ionizes to release H+ ion.
Acetic acid is an organic acid, which contains the acidic carboxyl group, -COOH.
When acetic acid (CH3COOH) ionizes, only the OH bond of the carboxyl group breaks, but
not the CH bonds. However, if one or more of the hydrogen atoms in the methyl group (CH3) is substituted with a more electronegative atom, the OH of -COOH group becomes
more polarized and ionizes more readily, and increasing the acidity. The following Ka values
illustrate the effect on the acidity of COOH when one or more of the methyl hydrogen is
substituted with more electronegative atoms:
CH3COOH(aq)
CH3COO-(aq) + H+(aq);
Ka = 1.8 x 10-5
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
ClCH2COOH(aq)
ClCH2COO-(aq) + H+(aq);
Ka = 1.4 x 10-3
FCH2COOH(aq)
FCH2COO-(aq) + H+(aq);
Ka = 2.6 x 10-3
chloroacetic acid
fluoroacetic acid
CCl3COOH(aq)
CCl3COO-(aq) + H+(aq);
trichloroacetic acid
Ka = 3.0 x 10-1
Exercise:
1.
Rank the following acids in order of increasing strength:
(a) CH3COOH, CH3CH2COOH, HCOOH;
2.
Metal oxides are either basic or have amphoteric properties. The oxides the Group IA
metals are strongly basic because they are generally very soluble in water. Other metal
oxides are less soluble, but they react with strong acids:
Na2O(s) + H2O(l) 2NaOH(aq);
P4O10(g) + 6H2O(l)
Al(OH)4-(aq);
Al(OH)3(s) + 3H3O+(aq)
[Al(H2O)6]3+(aq)
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
The hydrides of reactive metals, such as NaH and CaH2, are strong bases. The
hydride ion has a strong affinity for protons and reacts with water to produce hydroxide ions
and hydrogen gas:
H-(aq) + H2O(l) H2(g) + OH-(aq)
The Lewis Acids and Bases
According to G.N. Lewis, an acid is the reactant that is capable of sharing a pair of
electrons from another reactant to form a covalent bond; a base is the reactant that
provides the pair of electrons to be shared to form a covalent bond.
Based on the Lewiss definition, hydrogen ion (H+) is considered a Lewis acid and water and
ammonia are the Lewis bases in the following reactions:
H+ + H2O H3O+;
H+ + NH3 NH4+;
Lewis
Lewis
Lewis
Lewis
acid
base
acid
base
Species with incomplete octet (or electron deficient species) may act as Lewis acid and
those with lone pair of electrons may act as Lewis bases. For example, in the following
reactions, BF3, AlCl3, and FeBr3 are Lewis acids; while NH3, Cl-, and Br- are Lewis bases.
BF3 + NH3 F3B:NH3;
AlCl3 + Cl- AlCl4-;
FeBr3 + Br- FeBr4-;
In the formation of complex ions, the positive ions act as Lewis acids and the ligands
(anions or small molecules) are Lewis bases:
Cu2+(aq) + 4NH3(aq) Cu(NH3)42+(aq);
Lewis acid
Lewis base
H2CO3(aq)
H2SO4(aq)
(CH3)3N:AlCl3
Zn(OH)42-(aq);
AuCl4-(aq)
Acids Strength
H3O+(aq) + A-(aq)
Strong acids, such as HClO4, HCl, HNO3, and H2SO4, are those that are considered to
completely ionize at 1 M concentration. The above equilibrium would lie far to the right.
Acids that are only partially ionized at this concentration, such as HC2H3O2, HF, HNO2,
H2SO3, H3PO4, and HClO, are considered weak acids. Their dissociation equilibria would lie
far to the left.
The equilibrium constant, Ka, for the acid ionization is given by the following expression:
Ka
[H3O+][A-]
[H+][A-]
= =
[HA]
[HA]
MASTERING
PHYSICAL
1.
HF(aq)
2.
HNO2(aq)
3.
HC2H3O2(aq)
4.
HOCl(aq)
5.
HCN(aq)
CHEMISTRY
By-- S.K.SINHA
For strong acids, Ka would have a very large value; for weak acids, Ka < 10-1. The following
are the Ka values of some weak acids:
H+(aq) + F-(aq);
H+(aq) + NO2-(aq);
H+(aq) + C2H3O2-(aq);
H+(aq) + ClO-(aq);
H+(aq) + CN-(aq);
Strong acids have weak conjugate bases, and weak acids have strong conjugate
bases; the weaker the acid, the stronger will be its conjugate base. Likewise, weak bases
have strong conjugate acids; the weaker the base, the stronger will be its conjugate acid.
Examples:
HCl is a strong acid and Cl- is a very weak base;
According to Brnsted-Lowry, acid-base reactions favor the direction from strong acidstrong base combinations to weak acid-weak base combinations:
The following acid-base reactions go completely in the forward direction:
1.
2.
3.
+ CN (aq) HCN(aq) +
(HSO4- is a stronger than HCN)
Many acid-base reactions reach a state of equilibrium. The following acid-base reactions do
not go to completion; their equilibrium positions may shift to the right or to the left,
depending on the relative strength of the acid:
1.
HSO4-(aq)
SO42-(aq);
H2PO4-(aq) + C2H3O2-(aq)
HC2H3O2(aq) + HPO42-(aq);
Equilibrium shifts left; HC2H3O2 is the stronger acid and HPO42- is the stronger base.
2.
HNO2(aq) + C2H3O2-(aq)
HC2H3O2(aq) + NO2-(aq);
Equilibrium shifts right; HNO2 is the stronger acid, C2H3O2- is the stronger base.
Water as an Acid and a Base
Water is amphoteric because it can behave as an acid and a base. The following
equilibrium occurs in pure water:
H2O + H2O
Acid1 base1
H3O+(aq) + OH-(aq);
conjugate
acid2
conjugate
base1
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
The above equilibrium can be simplified as follows, which is also called the auto-ionization of
water:
H2O
H+(aq) + OH-(aq);
[H+] < 1.0 x 10-7 M, or [H+] < [OH-], the solution is basic;
[H+] = [OH-] = 1.0 x 10-7 M, the solution is neutral;
Exercise-2:
1.
What is [OH-] if [H+] = 0.0050 M? Is the solution acidic, basic or neutral?
2.
What is the [H+] if [OH-] = 6.0 x 10-4 M? Is the solution acidic, basic or neutral?
________________________________________________________________________
The pH Scale
pH is a scale that measures the acidity of an aqueous solution where [H+] is very small.
pH = -log[H+],
That is, if a solution has [OH-] = 1.0 x 10-7 M, pOH = -log(1.0 x 10-7) = -(7.00) = 7.00
Since, at 25oC, Kw = [H+][OH-] = 1.0 x 10-14
Thus, in aqueous solutions, if pH > 7.00 pOH < 7.00, and vice versa;
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
A strong base such as Ba(OH)2 produces twice the concentration of OH- as the concentration
of Ba(OH)2 in solution. Ba(OH)2 dissociates as follows:
Ba(OH)2(aq) Ba2+(aq) + 2OH-(aq);
[OH-] = 2 x [Ba(OH)2]
(a) pH = 4.50;
(b) pOH = 5.40
The pH of an HCl solution is found to be 3.00. To what final volume must a 100.-mL
sample of this acid be diluted so that the pH of the solution becomes 3.50? (316 mL)
4.
Initial [ ], M:
0.10
0.00
0.00
Change, [ ], M:
-x
+x
+x
Equilibrium [ ], M : (0.10 - x)
x
x
= 1.8 x 10-5
Since Ka << 0.10, we can use the approximation that x << 0.10, and (0.10 x) ~ 0.10
Then, Ka =
x2
~ x2/0.10 = 1.8 x 10-5 ;
(0.10 x)
x2 = (0.10)(1.8 x 10-5);
follows:
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
For strong acids, the percent dissociation at equilibrium is almost 100%. For weak acids, the
percent dissociation depends on Ka of the acid and their initial concentration. For example,
the percent dissociation of acetic acid (HC2H3O2, Ka = 1.8 x 10-5) at 0.10 M concentration is,
(1.3 x 10-3 M/0.10 M) x 100% = 1.3 %
Ka or pKa is a measure of the acid strength. The stronger the acid, the more of it
ionizes, and the greater its Ka (or the lower its pKa). The percent dissociation of a weak acid
then depends on its Ka and also on the degree of dilution. In the more dilute acid, a higher
percentage of the molecules will ionize.
Now consider a solution of 0.010 M acetic acid and its ionization products:
Concentration:
HC3H3O2(aq) H+(aq) + C2H3O2-(aq)
Initial [ ], M:
0.010
0.00
0.00
Change, [ ], M:
-x
+x
+x
Equilibrium [ ], M : (0.010 - x)
x
x
Ka << 0.010, we can still use the approximation that x << 0.010, and (0.010 x) ~ 0.010
Then, Ka =
x2
(0.010 x)
x2 = (0.010)(1.8 x 10-5);
Note that, the degree of ionization of the acid is higher in the more dilute acid solution. In
fact, in 1.0 M acetic acid, the percent dissociation is only 0.42%, which is a 10-fold lower
than in 0.010 M acid solution.
Exercise:
1.
What is [H+] in 0.10 M HNO2 solution and the pH of the solution? Ka = 4.0 x 10-4?
(Answer: [H=] = 6.3 x 10-3 M; pH = 2.20)
2.
A 0.10 M aqueous solution of lactic acid, HC3H5O3, has a pH = 2.43. Determine [H+] in
this solution and the Ka of lactic acid. (Answer: [H+] = 3.7 x 10-3 M; Ka = 1.4 x 10-4)
3.
If a 0.10 M benzoic acid, HC7H5O2 is 2.5% ionized, what is [H+] and pH of 0.10 M
benzoic acid? Calculate the Ka of benzoic acid.
(Answer: [H+] = 2.5 x 10-3 M; pH = 2.60; Ka = 6.4 x 10-5)
_________________________________________________________________________
Bases
Strong Bases:
Hydroxides of Group IA metals (LiOH, NaOH, KOH, RbOH, and CsOH) are strong
bases, but only NaOH and KOH are commercially important and are common
By-- S.K.SINHA
laboratory bases, since the others are quite expensive. These bases are quite soluble
in water and they completely dissociate in aqueous solution, producing a high
concentration of hydroxide ions. A moderately dilute solution of NaOH contains [OH-]
= Initial [NaOH].
NaOH(s) Na+(aq) + OH-(aq)
Among the hydroxides of the alkaline earth metals, Ca(OH)2, Sr(OH)2, and Ba(OH)2
are also relatively strong bases. When completely dissolved, these bases produce
two moles of OH- per mole of the base:
Ba(OH)2(aq) Ba2+(aq) + 2 OH-(aq)
[NH ][OH - ]
4
Kb =
= 1.8 x 10-5
[ NH 3 ]
The concentration of OH- of a weak base solution, such as NH3(aq), depends on its Kb and
the initial concentration of the base. For example, to determine [OH-], pOH and pH of 0.10
M NH3(aq), we can set up the following ICE table:
Concentration:
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
Initial [ ], M:
0.10
0.00
0.00
Change, [ ], M:
-x
+x
+x
Equilibrium [ ], M : (0.10 - x)
x
x
Kb = [NH4+][OH-] =
x2
= 1.8 x 10-5
[NH3]
(0.10 x)
Using approximation,
Kb =
(0.10 x)
x = (0.10)(1.8 x 10 );
2
-5
x2
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
11
Like weak acids, the percent dissociation of weak bases depends on the Kb of the base and
the degree of dilution larger Kb and higher dilution higher percent dissociation.
Exercise:
1.
What is [OH-] in 0.0055 M KOH and what is the pH of the solution?
2.
3.
CH3NH3+(aq) + OH-(aq)
_____________________________________________________________________
Polyprotic Acids
Acids such as HCl, HF, HOCl, HNO2, HC2H3O2, and other similar type of acids are
called monoprotic acids - each contains a single ionizable hydrogen ion. Some acids contain
more than one ionizable hydrogen, and they are called polyprotic acids. Examples of
polyprotic acids are H2SO4, H2SO3, H2C2O4, and H3PO4. In each case, the hydrogen ionizes in
stages and with different ionization constant, such as the following example with H3PO4:
H3PO4(aq)
H2PO4-(aq)
HPO42-(aq)
H+(aq) + H2PO4-(aq);
H+(aq) + PO43-(aq);
H+(aq) + HPO42-(aq);
Acid strength decreases in the order: H3PO4 >> H2PO4- >> HPO42-;
Sulfuric acid is a strong acid because the first hydrogen ionizes completely:
H2SO4(aq) H+(aq) + HSO4-(aq);
However, the second hydrogen does not dissociate complete. Thus, HSO4- is a weak acid,
which dissociates as follows:
HSO4-(aq) H+(aq) + SO42-(aq);
Ka2 = 1.2 x 10-2
Exercise:
1.
What is [H+], [HSO4-], and [SO42-] in 0.10 M H2SO4(aq)? What is the pH of the
solution? (Ka1 is very large; Ka2 = 1.2 x 10-2)
(Answer: pH = 0.96)
2.
What is the pH of 0.10 M oxalic acid, H2C2O4, and what is [C2O42-] in this solution?
(Ka1 = 6.5 x 10-2; Ka2 = 6.1 x 10-5 )
(Answer: [H+] = 0.054 M; pH = 1.26; [C2O42-] = 6.1 x 10-5 M)
_________________________________________________________________________
Acid-Base Properties of Salts
When salts (ionic compounds) dissolve in water, we assume that they completely dissociate
into separate ions. Some of these ions can react with water and behave as acids or bases.
Salts are also products of acid-base reactions. The acidic or basic nature of a salt solution
depends on whether it is a product of:
a strong acid-strong base reaction;
a weak acid-strong base reaction;
a strong acid-weak base reaction, or
a weak acid-weak base reaction.
By-- S.K.SINHA
Salts of Strong Acid-Strong Base Reactions: such as NaCl, NaNO3, KBr, etc.
This type of salt forms a solution that is neutral, because neither the cation ion nor
the anion reacts with water and offset the equilibrium between the H3O+ and OHconcentrations in the aqueous solution.
Salts of Weak Acid-Strong Base Reactions: such as NaF, NaNO2, NaC2H3O2, etc.
A salt that is the product of a reaction between a weak acid and a strong base will
form an aqueous solution that is basic in nature.
For example, Sodium acetate (NaC2H3O2) is a product of reaction between a weak acid
(HC2H3O2) and a strong base (NaOH).
HC2H3O2(aq) + NaOH(aq) NaC2H3O2(aq) + H2O(l)
When sodium acetate is dissolved in water, it dissociates into sodium and acetate ions:
NaC2H3O2(aq) Na+(aq) + C2H3O2-(aq)
HC2H3O2(aq) + OH-(aq);
Kb = [HC2H3O2][OH-]
[C2H3O2-]
Ka
Kw
(for HC2H3O2)
Thus, the hydrolysis of acetate ion has Kb = 5.6 x 10-10 (> Kw), which implies that the
solution of sodium acetate will be basic (pH > 7).
Salts of Strong Acid-Weak Base Reactions: NH4Cl, NH4NO3, (CH3)2NH2Cl, C5H5NHCl.
Aqueous solutions of this type of salts are acidic, because the cation (such as NH4+
ion) is the conjugate acid of a weak base (NH3)
the cations react with water, which increases [H3O+] in solutions.
For example, ammonium chloride, NH4Cl, is produced by the reaction of a strong acid HCl
and a weak base NH3.
HCl(aq) + NH3(aq) NH4Cl(aq) NH4+(aq) + Cl-(aq)
In an aqueous solution, ammonium ion (NH4+) establishes the following equilibrium that
increases [H3O+] and makes the solution acidic:
NH4+(aq) + H2O(l)
H3O+(aq) + NH3(aq);
Ka = [H3O+][NH3]
[NH4+]
For the reaction of NH3 with water, the following equilibrium occurs:
NH3(aq) + H2O(l)
NH4+(aq) + OH-(aq);
Kb = [NH4+][OH-]
[NH3]
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
Kw
=
Kb (for NH3)
13
-14
Thus, the hydrolysis of ammonium ion has Ka = 5.6 x 10-10 (> Kw), which implies that
aqueous solution of ammonium chloride will be acidic (pH < 7).
Salts of Weak Acid-Weak Base Reactions: such as NH4C2H3O2, NH4CN, NH4NO2, etc..
Aqueous solutions of this type of salts can either be neutral, acidic, or basic,
depending on the relative magnitude of the Ka of the weak acid and the Kb of the
weak base.
If Ka ~ Kb, the salt solution will be approximately neutral;
If Ka > Kb, the salt solution will be acidic, and
If Ka < Kb, the salt solution will be basic.
For example, Ka of HC2H3O2 = 1.8 x 10-5, Kb of NH3 = 1.8 x 10-5, and aqueous solution of
ammonium acetate, NH4C2H3O2, is approximately neutral.
NH4C2H3O2(aq) NH4+(aq) +
NH4+(aq) + H2O(l)
C2H3O2-(aq) + H2O(l)
C2H3CO2-(aq)
H3O+(aq) + NH3(aq);
HC2H3O2(aq) + OH-(aq);
Ka = 5.6 x 10-10;
Kb = 5.6 x 10-10;
Ka=Kb a neutral solution, because the hydrolyses result in a solution with [H3O+] = [OH-].
For NH4CN, Ka(HCN) = 6.2 x 10-10, Kb(NH3) = 1.8 x 10-5, and aqueous solution of NH4CN
will be basic.
NH4CN(aq) NH4+(aq) + CN-(aq)
NH4+(aq) + H2O(l)
H3O+(aq) + NH3(aq);
Ka = 5.6 x 10-10;
NO2-(aq) + H2O(l)
H3O+(aq) + NH3(aq);
HNO2(aq) + OH-(aq);
Ka = 5.6 x 10-10;
Kb = 2.5 x 10-11;
Ka > Kb acidic solution, because the hydrolyses result in a solution with [H3O+] > [OH-].
Calculating the pH of a Basic or an Acidic salt Solution
By approximation, [OH-] =
HC2H3O2(aq) + OH-(aq);
By-- S.K.SINHA
H3O+(aq) + NH3(aq);
By approximation, [H3O+] =
(a) KNO3
(b) CH3NH3Cl
(c) Na2SO3
(d) (NH4)2HPO4
Ka (for HSO3-) = 1.0 x 10-7; Ka (for H2PO4-) = 6.2 x 10-8; Kb (for CH3NH2) = 4.4 x 10-4
2.
3.
________________________________________________________________________
The Common Ion Effect in Acid-Base Equilibria
Common ions are ions produced by more than one solute in the same solution. For
example, in a solution containing sodium acetate and acetic acid, the acetate ion (C2H3O2-)
is the common ion. According to the Le Chatelier's principle, the following equilibrium for
acetic acid:
HC2H3O2(aq) + H2O(l)
H3O+(aq) + C2H3O2-(aq)
will shift to the left if C2H3O2- (from another source) is added to the solution. This will reduce
the acid dissociation, which lowers [H3O+] and increases the pH of the solution.
Addition of ammonium chloride, NH4Cl, to ammonia solution will cause the following
equilibrium to shift to the left:
NH3(aq) + H2O(l)
NH4+(aq) + OH-(aq)
NH4Cl dissociates to produce NH4+ and Cl- ions, where NH4+ is a common ion in the
equilibrium of ammonia solution. The introduction of NH4+ ion reduces the ionization of NH3,
which decreases [OH-] and lowers the pH of the solution.
Calculating [H+] and pH of a solution containing weak acid and the salt of its
conjugate base.
Consider a solution containing 0.10 M HNO2 and 0.050 M NaNO2, where the latter
dissociates completely as follows:
NaNO2(aq) Na+(aq) + NO2-(aq)
The concentration of H+ can be calculated using the following ICE table:
MASTERING
PHYSICAL
CHEMISTRY
Concentration:
HNO2(aq)
H+(aq) + NO2-(aq)
Initial [ ], M
0.10
0.00
0.050 (from salt)
Change, [ ], M
-x
+x
By-- S.K.SINHA
15
+x
Equilibrium [ ], M
(0.10 x)
x
(0.050 + x)
Ka =
Since Ka << 0.10,
[H ][NO -2 ]
( x)(0.050 x)
=
= 4.0 x 10-4
[HNO 2 ]
(0.10 - x)
x is assumed to very small, and by approximation,
( x)(0.050 x)
(x)(0.050)
~
= 4.0 x 10-4; x = 8.0 x 10-4
(0.10 - x)
(0.10)
[H+] = Ka x
[ HX ]
[X ]
Exercises:
1.
What are [H+] and pH of a solution containing 4.0 g of sodium acetate (NaC2H3O2) in
1.0 L of 0.050 M HC2H3O2(aq)? (Ka = 1.8 x 10-5 for acetic acid)
2.
What are [OH-], [H+], and pH of a solution containing 2.5 g of NH4Cl dissolved in 1.0 L
of 0.050 M NH3(aq)? (Kb = 1.8 x 10-5 for NH3)
Buffered Solutions
A buffered solution is one that has the ability to maintain its pH relatively constant even
when a small amount of strong acid or strong base is added.
Buffered solutions contain a comparable amount of weak acid and its conjugate base (or a
weak base and its conjugate acid).
Consider a buffer made up of acetic acid and sodium acetate, in which the major species
present in solution are HC2H3O2 and C2H3O2-.
If a little HCl is added to this solution, most of H+ (from HCl) is absorbed by the conjugate
base, C2H3O2-, in the following reaction:
H+(aq) + C2H3O2-(aq) HC2H3O2-(aq)
Since C2H3O2- is present in a much larger quantity than the added H+, the above reaction is
considered to go almost completely to the right. This buffering reaction prevents a
significant increase in [H+] and minimizes the change in its pH.
If a strong base such as NaOH is added, most of the OH- ions (from NaOH) are reacted by
the acid component of the buffer as follows:
OH-(aq) + HC2H3O2(aq) H2O + C2H3O2-(aq).
Again, because of the larger concentration of HC2H3O2 compared to OH-, this reaction also
goes almost to completion. This buffering reaction prevents a large increase in the [OH-]
and minimizes any change in the pH of the solution.
By-- S.K.SINHA
Buffer solution is generally prepared by dissolving a mixture of either a weak acid and a
"salt" that contains its conjugate base, or a weak base and a "salt" that contains its
conjugate acid, in the desired molar ratio to obtain the correct pH. A given buffer is effective
within a range of pH that is typically within approximately 1 of the pKa of its acid
component.
Examples of some common buffer systems:
Buffer
pKa
pH Range_____
HC2H3O2 NaC2H3O2
4.74
3.75 5.75
HCHO2 NaCHO2
KH2PO4 - K2HPO4
CO2/H2O NaHCO3
3.74
2.75 4.75
7.21
6.37
NH3 - NH4Cl
9.25
8.25 10.25
For a buffer containing the weak acid HB and the salt NaB, such that B- is the
conjugate base to the acid, the concentration [H+] and pH of the buffer depend on the
dissociation constant, Ka, of the acid component and the concentration ratio [B-]/[HB] in the
buffer solution.
Consider the equilibrium: HX(aq)
Re-arranging, we obtain,
H+(aq) + X-(aq);
[H+] = Ka x
Ka =
[ H ][ X ]
[ HX ]
[ HX ]
[ HX ]
; pH = pKa + log(
)
[X ]
[X ]
The last expression is called the Henderson-Hasselbalch equation, which is useful for
calculation the pH of solutions when the ratio [X-]/[HX] is known. For a given buffer
+
system, [H ] and pH varies with the ratio: [Base]/[Acid].
Exercise:
1.
A 100.0 mL buffer solution contains 5.0 g of 0.038 mol acetic acid and 0.061 mol of
sodium acetate. Calculate the pH of the buffer? (Ka = 1.8 x 10-5 for acetic acid)
If 0.0050 mol of HCl is added to the buffer, what is the final pH of the solution?
(Assume that the volume of buffer does not change when HCl(aq) is added.)
2.
3.
(a) Suppose you want to prepare a 100-mL buffer solution with pH = 7.30, which
buffer system would you consider? [Hint: look for acids that have pKa close to the
buffer pH.] (b) Calculate the ratio [Base]/[Acid] that the buffer should have. (c) If the
concentration of the acid is 0.50 M, what should be the base concentration?
(d) Assuming your starting materials are solids, how many grams of each must be
dissolved to make the 100. mL buffer solution? (Both acid and its conjugate base may
be in the form of sodium or potassium salts)
Buffering Capacity
The buffering capacity of a solution represents the amount of H+ and/or OH- the
buffer solution can absorb without significantly altering its pH. A buffer that contains large
concentrations of buffering components and able to absorb significant quantities of strong
acid or strong base with little change in its pH is said to have a large buffering capacity.
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
17
Whereas the pH of a buffered solution is determined by the ratio [X ]/[HX], buffer capacity is
determined by the sizes of [HX] and [X-] in the buffer.
-
1. Calculate the change in pH that occurs when 0.010 mol of HCl is added to 1.0 L of each
of the following buffers:
Buffer-A: 1.0 M HC2H3O2 + 1.0 M NaC2H3O2;
For these buffers the pH can be calculated using the Henderson-Hasselbalch equation:
pH = pKa + log([C2H3O2-]/[HC2H3O2]) = -log(1.8 x 10-5) + log(1) = 4.74
When 0.010 mol HCl is added to Buffer-A, the following reaction takes place:
H+(aq) + C2H3O2-(aq) ( HC2H3O2(aq)
[ ] before reaction:
0.010 M
1.0 M
1.0 M
[ ] after reaction:
0.99 M
1.01 M
The new pH = 4.74 + log(0.99/1.01) = 4.74 - 0.010 = 4.73 (pH is hardly changed ~ 0.21%)
When 0.010 mol HCl is added to Buffer-B, the following reaction takes place:
[ ] before reaction:
[ ] after reaction:
0
0.010 M
0.030 M
New pH = 4.74 + log(0.010/0.030) = 4.74 0.48 = 4.26 (pH decreases by 0.48 unit or 10%)
This shows that Buffer-A, which contains larger quantities of buffering components, has a much
higher buffering capacity that Buffer-B. For the Buffer-A to decrease its pH by 0.48 unit (or
10%), it would have to absorb the equivalent of 0.50 mol of HCl.
Exercise
1.
An acetate buffer solution is prepared by mixing 35.0 mL of 1.0 M HC2H3O2 and 65.0 mL
of 1.0 M NaC2H3O2. Calculate the pH of this buffer. If 1.0 mL of 6.0 M HCl is added to the
buffer solution, what will be the new pH of the buffer.
2.
A 100-mL buffer solution contains 0.20 M KH2PO4 and 0.32 M K2HPO4. What is the pH
of the buffer? If 0.0050 mol of HCl is added to the buffer without changing its volume,
what is the final pH of the buffer? (Ka = 6.2 x 10-8 for H2PO4-)
_________________________________________________________________________
Titration and pH Curves
By-- S.K.SINHA
Consider the titration of 20.0 mL of 0.100 M HCl with 0.100 M NaOH solution.
Calculate the pH of the solution: (a) before any of the NaOH is added; (b) after 15.0 mL of
NaOH is added; (c) after 19.5 mL of NaOH is added; (d) after 20.0 mL of NaOH is added;
(e) after 21.0 mL of NaOH is added.
(a) Before titration, [H+] = 0.100 M, pH = 1.000
(b) After 15.0 mL of NaOH is added, calculation of [H+] will be as follows:
H+(aq) + OH-(aq) H2O
[ ] before mixing:
0.100 M
0.100 M
[ ] after mixing, but
before reaction:
0.057 M
0.043 M
[ ] after reaction:
0.014 M
0.000
[ ] before mixing:
0.100 M
0.100 M
[ ] after mixing, but
before reaction:
0.051 M
0.049 M
[ ] after reaction:
0.002 M
0.000
[ ] before mixing:
[ ] after mixing, but
before reaction:
[ ] after reaction:
+ OH-(aq) ( H2O
0.100 M
0.100 M
0.050 M
0.000 M
0.050 M
0.000
At this point, the solution contains only water and salt (NaCl) and [H+] = [OH-] = 1.0 x 10-7 M,
which is due to water ionization. The pH of the solution will be 7.00 (pH of neutral solution)
(e) When 21.0 mL of 0.100 M NaOH has been added, there will be excess OH-:
H+(aq) + OH-(aq) ( H2O
[ ] after mixing, but
before reaction:
0.049 M 0.051 M
[ ] after reaction:
0.000
0.002 M
[OH-] = 0.002 M, ( pOH = 2.70, and pH = 11.30
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
19
Note that in strong acid-strong base titration, an abrupt change from about pH 3 to 11 occurs
within (0.5 mL of NaOH added near the equivalent point. All strong acid-strong base titration
have the same pH curves.
Weak Acid-Strong Base Titration
Net reaction: HX(aq) + OH-(aq) ( H2O + X-(aq)
For example, when acetic acid is titrated with sodium hydroxide, the net reaction is
HC2H3O2(aq) + OH-(aq) ( C2H3O2-(aq) + H2O
1. Consider the titration of 20.0 mL of 0.100 M HC2H3O2 with 0.100 M NaOH solution.
Calculate the pH of the solution: (a) before any of the NaOH is added; (b) after 10.0 mL
of NaOH is added; (c) after 15.0 mL of NaOH is added; (d) after 20.0 mL of NaOH is
added; (e) after 25.0 mL of NaOH is added.
Solution:
Concentration, M:
HC2H3O2(aq) + OH-(aq) C2H3O2-(aq) + H2O
Before mixing:
0.100
0.100
0.000
After mixing, before rxn:
0.0667
0.0333
0.000
After reaction:
0.0333
0.000
0.0333
[HC 2 H 3 O 2 ]
(0.033 M)
= 1.8 x 10-5 x
= 1.8 x 10-5 M
(0.033 M)
[C 2 H 3 O 2 ]
pH = pKa + log(
[C 2 H 3 O -2 ]
= 4.74 + log(1) = 4.74
[C 2 H 3 O 2 ]
When a weak acid is half-neutralized, 50% of the acid is converted to its conjugate base.
That is, at half-way to the equivalent point of the titration, [C2H3O2-] = [HC2H3O2]. Under
this condition, [H+] = Ka, and pH = pKa.
(c) At the equivalent point (when 20.0 mL of 0.100 M NaOH has been added), all of the acid
is converted to its conjugate base. The latter undergoes hydrolysis as follows:
C2H3O2-(aq) + H2O(l)
HC2H3O2(aq) + OH-(aq)
Initial [ ], M:
0.0500
0.000
0.000
Change, [ ], M:
-x
+x
+x
Equilibrium [ ], M: (0.0500 x)
x
x
By approximation, [OH-] = x =
K b x [C 2 H 3 O -2 ]0 =
By-- S.K.SINHA
The hydrolysi of the conjugate base of a weak acid produces OH , which leads to pH > 7 at
the equivalent point. In the case of acetic-NaOH titration, the pH at the equivalent point is
about 8.72. The larger the Ka of the weak acid, the closer the pH to 7 at equivalent point.
The smaller Ka, the higher the pH than 7 at equivalent point.
-
Exercise
1.
In a titration of 20.00 mL of 0.100 M formic acid, HCHO2, with 0.100 M NaOH,
calculate the pH: (a) before NaOH was added; (b) after 15.00 mL of NaOH is added;
(b) after 20.00 mL of NaOH is added. (Ka = 1.8 x 10-4 for HCHO2)
2.
In a titration of 20.00 mL of 0.100 M NH3(aq) with 0.100 M HCl(aq), calculate the pH:
(a) before titration begins; (b) after 10.0 mL of HCl(aq) is added; (c) at equivalent
point, that is after 20.0 mL of HCl(aq) is added. (Kb = 1.8 x 10-5 for NH3)
_________________________________________________________________________
The Use of Indicators in Acid-Base Titration
Like a weak acid, an indicator exhibits the following equilibrium in aqueous solution:
HIn(aq)
Ka =
H+(aq) + In-(aq);
[H ][In - ]
;
[HIn]
[In - ]
)
[HIn]
[In - ]
) = pKa - 1; indicator assumes the color of acid form
[HIn]
[In - ]
pH = pKa + log(
) = pKa + 1; indicator assumes the color of base.
[HIn]
Phenolphthalein, which is the most common acid-base indicator, has Ka ~ 10-9. Its acid form
(HIn) is colorless and the conjugate base form (In-) is pink. It is colorless when the solution
pH < 8, that is when 90% or more of the species are in the acid form (HIn), and pink at pH
> 10, when 90% or more of the species are in the conjugate base form (In-). The pH range
at which an indicator changes depends on the Ka. For phenolphthalein with Ka ~ 10-9, its
color changes at pH = 8 10. It is suitable for strong acid-strong base titration and weak
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
21
acid-strong base titration. The range of pH for other common acid-base indicators are listed
below:
Indicators:
Methyl orange
Acid Color
orange
Base Color
yellow
pH Range
3.2 4.5
Type of Titration
strong acid-strong base
strong acid-weak base
Bromocresol green
yellow
blue
3.8 5.4
Methyl red
Red
Yellow
4.5 - 6.0
Bromothymol blue
Yellow
blue
6.0 - 7.6
Phenol Red
orange
red
6.8 8.2
Solubility Equilibria
Solubility Equilibria and the Solubility Product Constants
When a slightly soluble salt such as silver chloride, AgCl, is dissolved in water, a
saturated is quickly obtained, because only a very small amount of the solid dissolves, while the
rest remains undissolved. The following equilibrium between solid AgCl and the free ions occurs
in solution:
AgCl(s) Ag+(aq) + Cl-(aq);
Ksp = [Ag+][Cl-]
aMb+(aq) + bXa-(aq),
Ksp = [Mb+]a[Xa-]b
A. For ionic equilibria of the type: MX(s)
Mn+(aq) + Xn-(aq);
Ksp = [Mn+][Xn-]
Ba2+(aq) + SO42-(aq);
[Ba2+] = [SO42-] = S mol/L, Ksp = S2; and S = (Ksp) = (1.5 x 10-9) = 3.9 x 10-5
mol/L
B. For ionic equilibria of the type: MX2(s)
and for the type:
M2X(s)
M2+(aq) + 2X-(aq),
2 M+(aq) + X2-(aq);
Ksp = [M2+][X-]2 ;
Ksp = [M+]2[X2-]
Ca2+(aq) + 2F-(aq);
The solubility of calcium fluoride is S = (Ksp/4)1/3 = (4.0 x 10-11/4)1/3 = 2.2 x 10-4 mol/L
By-- S.K.SINHA
M3+(aq) + 3X-(aq),
3 M+(aq) + X3-(aq),
Ksp = [M3+][X-]3
Ksp = [M+]3[X3-]
3Ag+(aq) + PO43-(aq);
( K sp / 27)
S=
( K sp / 27) =
2M3+(aq) + 3X2-(aq),
Ksp = [M3+]2[X2-]3
3M2+(aq) + 2X3-(aq),
Ksp = [M2+]3[X3-]2
If the solubility of the compound M3X2 is S mol/L, then [M2+] = 3S, and [X3-] = 2S;
Ksp = (3S)3(2S)2 = 108S5; S =
For example, Ca3(PO4)2(s)
K sp / 108
3Ca2+(aq) + 2PO43-(aq),
1. Suppose the solubility of PbSO4 in water is 4.3 x 10-3 g/100 mL solution at 25 oC. What
is the Ksp of PbSO4 at 25 oC?
Solution:
Solubility of PbSO4 in mol/L = 4.3 x 10-3 g x 1000 mL/L = 1.40 x 10-4 mol/L
100. mL
303.26 g/mol
That is, a saturated solution of PbSO4, contains [Pb2+] = [SO42-] = 1.4 x 10-4 mol/L
For the equilibrium: PbSO4(s)
Pb2+(aq) + SO42-(aq);
_________________________________________________________________________
Determining Solubility from Ksp
1.
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
23
Mg2+(aq) + 2 OH-(aq)
K sp / 4 =
Exercise:
1.
The Ksp of PbI2 is 1.4 x 10-8. What is its solubility in grams per 100. mL of solution at
25oC?
2.
Calcium hydroxide, Ca(OH)2, has Ksp = 1.3 x 10-6. How many grams of Ca(OH)2 can be
dissolved in 250-mL solution to make a saturated solution at 25oC?
_________________________________________________________________________
Relative Solubility from Ksp
For compounds whose formula yields the same number of ions, their Ksp value can be
used to determine relative solubility. That is, larger Ksp implies greater solubility.
Common Ion Effect of Solubility
The presence of common ion decreases the solubility of a slightly soluble ionic
compound. For example, in the following equilibrium
PbCl2(s)
Pb2+(aq) + 2 Cl-(aq)
If some NaCl is added to a saturated solution of PbCl2, the [Cl-] will increase, and according
to Le Chatelilers principle, the equilibrium will shift in the direction that tends to reduce [Cl]. In this case, the equilibrium will shift left, to form more PbCl2 solid, hence decreasing the
amount of PbCl2 that dissolves into solution.
Sample Problem
The Ksp of BaSO4 is 1.5 x 10-9 at 25 oC. (a) What is its solubility in water at 25oC? (b)
What is the solubility in 0.10 M Na2SO4 at 25 oC?
Solubility equilibrium for BaSO4: BaSO4(s)
Ba2+(aq) + SO42-(aq);
x mol/L
pH affect the solubility of slightly soluble compounds containing anions that are
conjugate bases of weak acids, such as F-, NO2-, OH-, SO32-, and PO43-, but not those
containing anions which are conjugate bases of strong acids, such as SO42-, Cl-, Br-. For
example, in a saturated solution of calcium fluoride, CaF2, the following equilibrium exists:
By-- S.K.SINHA
Ca2+(aq) + 2F-(aq)
When a strong acid is added to the saturated solution, the following reaction occurs:
H+(aq) + F-(aq) HF(aq)
This reaction has the net effect of reducing the concentration of F- ions, which causes the
equilibrium to shift to the right and resulting in more of CaF2 to dissolve.
Exercise
1.
Calculate the solubility of PbCl2 (Ksp = 1.6 x 10-5) and AgCl (Ksp = 1.6 x 10-10) in 0.010
M NaCl solution.
2.
What is the solubility of CuS (Ksp = 4 x 10-37) and ZnS (Ksp = 2 x 10-25), respectively,
in solution buffered at pH = 8.00? (For H2S, Ka1 = 1 x 10-7; Ka2 = 1 x 10-19)
_________________________________________________________________________
Precipitation and Qualitative Analysis
aM+(aq) + bX-(aq),
Sample problem:
If 20.0 mL of 0.050 M Pb(NO3)2 is mixed with 30.0 mL of 0.10 M NaCl, will PbCl2
precipitate form? Ksp of PbCl2 = 1.6 x 10-5.
Pb2+(aq) + 2Cl-(aq)
[ ] after mixing
0.020 M
PbCl2(s)
0.060 M
Exercise:
1.
At what pH a solution containg 0.10 M Ca2+ ions will form a precipitate of Ca(OH)2?
(Ksp = 1.3 x 10-6 at 25 oC for Ca(OH)2)
2.
Will Ag2SO4 precipitate if 30.0 mL of 0.050 M AgNO3 is added to 20.0 mL of 0.10 M of
Na2SO4 solution? Ksp = 1.2 x 10-5 for Ag2SO4 at 25oC.
_________________________________________________________________________
Practical Application of Ionic Equilibria
Qualitative Analysis
The presence of certain ions, such as Cl-, I-, SO42-, Ag+, etc. in water can be
determined qualitatively and quantitatively by precipitation method. Cl- and I- can be
precipitated as AgCl and AgI, respectively, by adding AgNO3 solution.
Synthesis
Certain industrial chemicals, such as AgCl, AgBr, AgI, that are needed in
photographic industries are prepared by precipitation.
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
25
Since the Ksp of these compounds are very small, the precipitation reaction practically goes
to completion. The separation and purification processes are simple.
Selective Precipitation
A solution contains 0.10 M in Cl- and 0.010 M in I-. At what concentration of Ag+
would (a) AgI begin to precipitate; (b) AgCl begins to precipitate? What is the
concentration of I- when AgCl begins to precipitate? (Ksp[AgCl] = 1.6 x 10-10 and
Ksp[AgI] = 1.5 x 10-16)
3.
By-- S.K.SINHA
[HS ] very low, which precipitates only the following group of cations: Cu2+, Cd2+, Hg2+,
Sn2+, and Bi3+. Centrifuging and decanting gives the next solution.
-
Ion group 3: Base-insoluble sulfides. The supernatant from acidic sulfide treatment is
treated with NH3/NH4+ buffer to make the solution slightly basic (pH~8). The excess OH- in
solution increases [HS-], which causes the precipitation of the more soluble sulfides and
some hydroxides. The cations that precipitate under this condition are: Zn2+, Mn2+, Ni2+,
Fe2+, Co2+, as sulfides, and Al3+, Cr3+, and Fe3+ as hydroxides. The precipitate is centrifuged
and the supernatant decanted to give the next solution.
Ion group 4: Insoluble phosphates. The slightly basic supernatant separated from the
group 3 ions is treated with (NH4)2HPO4, which precipitates Mg3(PO4)2, Ca3(PO4)2, and
Ba3(PO4)2.
Ion group 5: Alkali metal and ammonium ions. The final solution contains any of the
following ions: Na+, K+, and NH4+.
Sample qualitative analysis.
A solution contains a mixture of Ag+, Al3+, Cu2+, and Fe3+ ions. Devise a scheme to
separate and identify each of these cations.
Mixture: Ag+, Al3+, Cu2+, Fe3+ (colored solution)
add 3 M HCl,
centrifuge
Precipitate (white)
AgCl
Supernatant (colored)
(Al3+, Cu2+, Fe3+)
add 6 M NaOH,
centrifuge
Precipitates
(Cu(OH)2 & Fe(OH)3)
add 6 M NH3
Precipitate
Fe(OH)3
(dark brown)
Supernatant (colorless)
Al(OH)4-
Supernatant
Cu(NH3)42+
(dark blue)
______________________________________________________________________________
Complex Ion Equilibria
15.8 Equilibria Involving Complex Ions
MASTERING
PHYSICAL
CHEMISTRY
By-- S.K.SINHA
27
A complex ion consists of a central metal ion that is covalently bonded to two or
more ligands, which can be anions such as OH-, Cl-, F-, CN-, etc. or neutral molecules such
as H2O, CO, and NH3. For example, in the complex ion [Cu(NH3)4]2+, Cu2+ is the central
metal ion with four NH3 molecules covalently bonded to it.
All complex ions are Lewis adducts; the metal ions act as Lewis acids (electron-pair
acceptors) and the ligands are Lewis bases (electron-pair donors). Only species with at least
one lone-pair electrons can be a ligand.
The Formation of Complex Ion
In aqueous solutions, metal ions form complex ions with water molecules as ligands.
When another ligand is introduced into the solution, ligand exchanges occur and equilibrium
is established. For example, when NH3 is added to aqueous solution containing Cu2+ ion, the
following equilibrium occurs:
Cu(H2O)62+(aq) + 4 NH3(aq)
Kf =
[Cu(NH3)4]2+(aq) + 6H2O
[Cu(NH 3 ) 24 ]
[Cu(H 2 O) 62 ][NH 3 ] 4
At molecular level, the ligand exchange process occurs in stepwise manner; water
molecule is replace with NH3 molecule one at a time to give a series of intermediate species,
each with its own formation constant. For convenience, the water molecules can be omitted
from the equation.
1.
Cu2+(aq) + NH3(aq)
Kf1 =
2.
Cu(NH3)2+(aq);
[Cu(NH 3 ) 2 ]
[Cu 2 ][NH 3 ]
Cu(NH3)2+(aq) + NH3(aq)
Kf2 =
3.
Cu(NH3)22+(aq);
[Cu(NH 3 ) 22 ]
[Cu(NH 3 ) 2 ][NH 3 ]
Cu(NH3)32+(aq) + NH3(aq)
Kf4 =
Cu(NH3)42+(aq);
[Cu(NH 3 ) 24 ]
[Cu(NH 3 ) 32 ][NH 3 ]
The overall formation constant is the product of all intermediate formation constants:
[Cu(NH 3 ) 24 ]
Kf = Kf1 x Kf2 x Kf3 x Kf4 =
[Cu 2 ][NH 3 ]4
Kf is called the formation constant for the complex equilibrium.
Sample problem-4:
If a 30.0-mL solution containing 0.020 M Cu2+ is mixed with 20.0 mL of 0.20 M NH3
solution, what is the concentration of Cu2+ in solution? Kf = 5.0 x 1012
By-- S.K.SINHA
Solution: First calculate the concentration of each species in the solution after mixing, but
before formation of complex ion Cu(NH3)42+:
[Cu2+] = 0.020 M x (30.0 mL/50.0 mL) = 0.012 M
[NH3] = 0.20 M x (20.0 mL/50.0 mL) = 0.080 M
Cu(NH3)42+(aq) + 4 H2O
Since Kf is very large, we can assume that all of Cu2+ is converted to Cu(NH3)42+.
Then, [Cu(NH3)42+] = 0.012 M and [NH3] = 0.080 M (4 x 0.012 M) = 0.032 M
Next, consider the following (reverse) equilibrium:
Cu(NH3)42+(aq)
Kc =
Cu2+(aq) + 4NH3(aq)
[Cu 2 ][NH 3 ]4
[Cu(NH 3 ) 24 ]
Concentration (M)
Cu(NH3)42+(aq) Cu2+(aq) + 4 NH3(aq)
Initial:
0.012 M
0.000
0.032 M
Change:
-x
+x
+x
Equilibrium:
(0.012 x)
x
(0.032 + x)
( x)(0.032) 4
= 2.0 x 10-13;
(0.012)
Ligand increases the solubility of slightly soluble ionic compounds if they form
complex ions with the metal ions. For example, silver chloride, AgCl, is more soluble in
ammonia solution because silver ions form complex ions with NH3:
AgCl(s)
Ag+(aq) + Cl-(aq);
AgCl(s) + 2NH3(aq)
Ag(NH3)2+(aq) + Cl-(aq);
Ag+(aq) + 2NH3(aq)
Ag(NH3)2+(aq);
Exercise:
1.
Calculate the solubility (a) in mol/L and (b) in g/L of AgCl in 2.0 M NH3(aq). What is the
concentration of Ag+ in this solution? (Ksp = 1.6 x 10-10; Kf = 1.7 x 107 for Ag(NH3)2+)
2.
Will AgCl precipitates form if 5.0 mL of 0.10 M AgNO3 is added to 5.0 mL of solution
containing 0.10 NaCl and 2.0 M NH3? (b) Will precipitate form if [NH3] = 1.0 M?
3.
MASTERING
PHYSICAL
CHEMISTRY
Ag+(aq) + S2O32-(aq)
Ag(S2O3)-(aq) + S2O32-(aq)
Ag+(aq) + 2S2O32-(aq)
Ag(S2O3)23-
By-- S.K.SINHA
29
Ag(S2O3)-;
Ag(S2O3)23-(aq);
Ag(S2O3)23-(aq);
Miscellenius Problems
PROBLEM. 1.
A chemist needs to prepare about 400 mL of a buffer solution of pH
5.0 using acetic acid. What should the weight of sodium acetate (MW 82.034 g/mole)
should be added to 400 mL of 0.1 M acetic acid (MW 60.052 g/mole) solution to prepare
the buffer? (Ka=1.75X10-5 for acetic acid.)
Ans 5.76 gram
PROBLEM. 2 20 mL of a diprotic acid, H2A, is titrated with 0.1 M NaOH titrant. The
resulting titration curve is shown below.
(a) Label the two points where the solution has the maximum buffer capacity and label
first and second equivalence points as .
(b) Estimate the formal concentration of H2A from the graph.
(c) There are simple expressions for the pH at points A, B, and C. Give the equations
below.
(d) Estimate Ka1 and Ka2 for this acid from your estimate of pH at points A, B, and C.
(e) At what indicator pH would you want your color-change indicator to have in order to
titrate to the second equivalence point?
Ans (a) Buffer capacity at A & C
1st equivalence point at B 2nd at D.
(b) 0.1 M
By-- S.K.SINHA
(D)
(e)At pH=10
PROBLEM. 3.Calomel, Hg2Cl2, (MW 472.09) dissolves to form Hg22+ and chloride with
a Ksp=1.2 10-18. Calculate the mass of calomel that will dissolve in...
A.
Hg2Cl2 s)<=>Hg2+
2 (aq) + 2Cl (aq)